Secondary alcohol production



Feb. 22, 1938. F. M. ARCHIBALD Er AL 4 SECONDARY ALCOHOL PRODUCTION 1Filed Aug-12, 195a I 23 (-9 ACID 072 WATER l /ILET Ricrcmt ACAD- L/NE Il5 HYDROCARBON OUTLET OLEFIN OUTLET I ETHER OUTLET OLEFIN .BxsAiE/wq fix0120:4230

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Patented Feb. 22, 1938 I I UNITED STATES PATENT OFFICE 2,109,004SECONDARY i LoonoL PRODUCTION Francis M. Archibald, Elizabeth, andHelmuth G. Schneider, Roselle, N. J., assignors to Standard AlcoholCompany Application August 12,1936, Serial No. 95,578

v '7 Claims. (Cl. 260-156) This invention relates to an improved processcarry out the process of the invention andindifor producing an alcoholdirectly from an olefin oates the fiow of materials. and relates moreparticularly to a catalytic Referring to the drawing, numeral p processfor producing an alcohol from an olefin sents an absorption .tower. Thistower is procontaining two to five carbon atoms. It may vided with acidplates 2 or other means whereby 5 likewise be used to produce alcoholfrom an olegood contact of the catalytic material and the fin containingup to seven carbon atoms or more, olefinic material is obtained. Thecatalytic It is known that olefins may be reacted with materialpreferably used according to this incatalytic materials to form reactiveacid liquors, vent o s an aqueous solution o ulf acid the reactive acidliquors diluted, hydrolyzed and f 50 o 7 concentration w n p py ne i 10distilled to obtain alcohols. The catalytic matethe olefin being re h rconcentrations rial generally used is sulfuric acid, though other f aqic acid p to and lower catalytic materials have been used, for example,concentrations to m y be used h pr pyl n phosphDriC acid, hydrochloricacid, acetic m and the other olefins. While aqueous sulfuric l5 andother acids, and also aqueous solution of aeidisthe preferred Catalyst.other aqueous s usalts such as zinc chloride, aluminum chloride, ons ofcatalytic material y e u e or 6X- etc., of the concentrations at whichthey are cap e, aqueous solutions of phosphoric acid, ypable of formingreactive acid liquors. drochloric acid, zinc chloride, aluminumchloride, It has been found that olefins on reactin with etc. It is notnecessary to use the diluted sulfuric catalytic materials of definiteconcentration and id as such in'the absorption tower as reactive 20temperatures form alkyl sulfates, alcohols and c liquor diluted to belowp e ab y ab ut ethers directly. It has been shown in c'opend- 50% to70%, may be d- The q u catalytic ing application, Serial No. 83,894,Production of material is maintained at substantially the same ethersdirectly from olefins", filed June 6, 1936, concentration hroughout theprocess. by H. G. Schneider, that after certain amounts of The olefin,or m re of fi if i tu e of 2 al yl sulfates, alcohols and ethers areformed, difi'erent alcohols is to be made, substantially the reactionreaches an equilibrium, If the pure or in a hydrocarbon mixturecontaining the ,ethers thereby produced are removed and the desiredolefin OI OlBfiIlS, lS'piSSBd into thebottom amount of others in theacid solutions maintained of absorption tower l by means of p This atlow concentration, the e uilibrium is disturbed. olefin is passed intothe bottom of the absorption 30 Substantially all of the oleiinsthereafter passed tower I under a partial p ss f e lefin into the olefinacid liquor are converted into of at least 2 Pounds p square c P essu esethers if .the ethers are removed continuously as of 40 to 200 morepounds D Square inch P they ar formed, tlal pressure of the olefin arepreferred though 5 According to this invention, it has been found higherand lower pressures may be used. It is that alcohol is formed directlywhen an olefin is not necessary that the olefin b in Vapor Phasecontacted with an aqueous hydrating catalyst of as Olefin in the liquidPhase may also be used to ammt t t and t, certain t produce alcoholaccording to this invention. tures and pressures, and after the alcoholis sepa- The olefin pa ses upwardly through the ab- 40' rated from thecatalytic material the catalytic sorption tOWeT I through the aqueousSulfuric 0 material reacts with more of the olefin added to acid layerson the acid plates on layers may be form more alcohols. Ether is alsoformed which maintained on the top of the aqueous catalytic may beSeparated from the catalytic material acid layers if desired in order toobtain better congether with the alcohol. The preferred method tact thei and the olefin An outlet pipe of separating the alcohol or a mixtureof alcohol a prmflded wlth valve 5 removes.the unrefacted 45 materials.The aqueous catalytic material is and ether from the catalytic materialis by steam passed/into the abior tion tower l thmu h i stripping thoughthey may be distilled ofi without p g p pe th dam f S 1 t 6 and whileflowing downward through the ab- 6 a on 0 Steam 0 extrac 1011 maysorption tower is contacted with the olefin matealso L rial. The aqueouscatalytic material with the 50 The invention will be more fullyunderstood on reaction products in solution is passed through" readingthe following description with reference pipe 1 into t tripping tower a,The absorption to the accomp nying drawingtower is maintained at atemperature of 30 C. The drawing shows a diagrammatic view in or higherby means of coil 9 or other heat consectional elevation of an apparatusadapted to trolling means. The preferred temperature when 55 means ofpump l8 into pipe 6 isopropyl alcohol is being produced is about 80 to130 C. By the use of these temperatures, pressures, and catalyticconcentration all of the oleflns present are reacted in one pass.Stripping tower 8 is provided with a. steam coil in and also an opensteam spray outlet H, whereby the temperature may be raised to thedistilling temperature of the alcohol and ether and the concentration ofthe acid controlled. The vapors of alcohol and ether are removed throughoutlet I! and fractionated in tower is if desired, condensed and passedto storage.

The separated ether is preferably recycled back into the olefin materialthat is passed into the absorption tower i, by means of pipe 3 thoughboth alcohol and ether may be passed to storage. The separated sulfuricacid in is withdrawn through line it and passed by and thereby into theabsorption tower i. when the open steam spray outlet is not used toremove the alcohol and ether and at the same time to maintain the acidat the desired concentration; water is added to the acid as it enterspipe 5 before it is re-' turned to the absorption tower i through pipei3 provided with valve M. The acid is used continuously, being recycledto the absorption tower after the alcohol and ether are stripped out,

though it may be necessary to add small amounts of the acid and waterthrough pipe is provided with valve i l to maintain the desired volumedue to slight losses, and also to maintain the desired concentration.

The following table shows the yields of isopropyl alcohol and isopropylether obtained on reacting propylene and aqueous sulfuric acid ofdifferent concentrations and at different temperatures and pressure overvarious lengths of time:

, Products per 0 Pam! Tim tg-l of i il oncenpressure 9 0 ac tration ofTem 01 proof con sulfuric. mm ylene, tact d used Wax acid, 8mm l s. rhhours M01 of Mel.

alcohol other Percent 0.

55 Oil present.-..- 110 190 1 4 1. 37 0. 193 55 Oil present-- 110 1902 1. 51 0.311 65 Oil present-.... 110 190 4% 1. 79 0. B8 60 Oilpresent... 100 190 1 1.54 0.191 60 Oil present--- 100 191) 1. 73 0. 34360 Oil present.... 100 190 4% 1. 96 0. 670 60 No oil present. 100 190 1.l5 0. 150 60 No 011 present. 100 100 4% 1. 94 0. 72 60 Oil present----170 1. 42 0. 088 60 Oil present. 90 170 2 1. 716 0. 204 60 Oilpresent.... 90 170 4% 1. 986 0. 32 60 Oil present..- 90 1 1. 0. 60 Oilpresent. 100 90 2 1. 330 0:218 60 01] present. 100 90 4} .1. 390 0. 28670 Oil present. 100 190 1. 670 0. 463 70 Oil present.-.- 100 100 1. 6000. 575

Alternately a second absorption tower may be provided into which theether and oleflns sepmay be used in this absorption tower. The seturatedacid from theflrst absorption tower may be used that is by being passedin countercurrent relation to the ether and olefin to obtainsupersaturated solution.

The foregoing description is merely illustrative and various changes andalternative arrangements may be made. It is not the intention to limitthe process to the exact temperatures, pressures and acid concentrationsthat are given but to limit it within the scope of the appended claims,in which it is my intention to claim all stripping tower 8.

which pressure of 40 to 269 pounds inherent novelty as permits.

We claim: a

1. A process for manufacturing an alcohol from an olefin which comprisescontacting an olefin with an aqueous solution of sulfuric acid, of 1% to84% concentration and under a partial initial pressure of the olefinabove 2 lbs. per square inch, and a hydration temperature above 30? 0.,separating the aqueous solution of sulfuric acid, stripping the aqueoussolution by means of steam of the alcohol and ether that-are in solutionand at the same time avoiding any dilution or concentration of thesulfuric acid so that it is of constant concentration and recontactingthe residual aqueous solution of sulfuric acid of 1 to 84% concentrationwith another portion of the bmadlyasthepnorart v olefin to furthermanufacture more of the alcohol.

the ether is recirculated with the aqueous solution of sulfuric acid.

3. A process for manufacturing isopropyl alcohol from propylene whichcomprises continuously passing propylene countercurrently to an aqueoussolution of sulfuric acid of about 50 to 70% concentration whereby asubstantial amount of isopropyl alcohol is formed directly and is insolution in the aqueous solution of sulfuric acid, continuouslywithdrawing the aqueous sulfuric acid with the isopropyl alcohol insolution, continuously separating the isopropyl alcohol from the aqueoussulfuric acid while maintaining the aqueous sulfuric acid at the sameconcentration of about 50 to 70% and continuously recycling the aqueoussulfuric acid countercurrently with more of the propylene.

a. A process for manufacturing isopropyl alcohol from propyleneaccording to claim 3 in per square inch and temperature of 60 to 6. aremaintained.

5. A process for manufacturing an alcohol from an olefin comprisingcontacting an olefin with an acid liquor that had been prepared bycontacting an olefin with concentrated sulfuric acid and diiuted to aconcentration less than 29%, whereby an alkyl ester,v alcohol and etherare formed directly, separating the alcohol from the aqueous solution ofthe hydrating catalyst while substantially maintaining the concentradonof the hydrating catalyst constant and contacting more of the olefinwith the aqueous solution of the hydrating catalyst.v

6. A process for manufactu ing an alcohol from an olefin which comprisespassing a mixture of hydrocarbons containing clenns in counter-currentrelation to an aqueous solution of sulfuric acid of less than 70%concentration whereby substantially complete removal of the olefin fromthe hydrocarbon mixture arating the alcohol, ether and an olefin fromthe aqueous solution of sulfuric acid while maintaining theconcentration of the sulfuric acid substantially constant and contactingmore of the hydrocarbon mixture containing olefin together with the saidether and olefin that had been separated with the aqueous solution ofsulfuric acid to form alcohols.

v 7. A process for manufacturing an alcohol from an olefln whichcomprises contacting an olefin together with oil with an aqueoussolution of sulfuric acid of 1% to 84% concentration and under a partialinitial pressure of the olefin above escapee 3 2 lbs. per square inch,and a hydration temberature above 30 0., separating the aqueous solutionof sulfuric acid, stripping the aqueous solution by means of steam ofthe alcohol and other that are in solution and. at the same timeavoiding any dilution or concentration of the'sulfuric acid so that itis of constant concentration and.

recontacting the residual aqueous solution of suifuric acid of 1 to 84%concentration with another portion of the olefin to further manufacturemore of the alcohoL-

